Studies in Flame Retardancy of Polymers - American Chemical Society

Chapter 32

X-ray Photoelectron Spectroscopy (Electron Spectroscopy for Chemical Analysis) Studies in Flame Retardancy of Polymers Downloaded by NATL UNIV OF SINGAPORE on March 27, 2017 | http://pubs.acs.org Publication Date: July 21, 1995 | doi: 10.1021/bk-1995-0599.ch032

Jianqi Wang National Laboratory of Flame Retarded Materials, College of Chemical Engineering and Materials Science, Beijing Institute of Technology, Beijing 100081, China Thermal aggradation of polymers and subsequent events (e.g. burning) occur rationallyfirstfromthesurfaceexposedto be beat fluxfromsurroundingsand then go further in depth. This article aims at introducingandexemplifying the potential applications of XPS, a surface sensitivetool,inflameretardencyof polymers, such as, thermal degradation,structuralidentification, synergisms, and charring processes in condensed phase. Being coupled with other techniques C1s andO1sdata about charring which can hardly be dealt with by conventional techniques were particularly provided and described. The amazing growth and diversification of surface analysis techniques began in the 1960 with the development of electron spectroscopy -firstAuger spectroscopy (AES), thenfollowedfayX-ray Photoelectron Spectroscopy (XPS, or ESCA, Electron SpectroscopyforChemical Analysis). Recently, these techniques haverapidlymatured with the generation of a large volume of literature and are nowroutinelyused in industry and universities providing a wealth ofinformation,e.g. elemental competition, detailed knowledge of chemical bonding states, and depth profiles of the outermost atomic layers of solids. Application of XPStotheStudy of Flame Retardancy of Polymers Polymers are increasingly pervasiveinmaterialscience.theimpactofXPSon materials characterization of polymers has been twofold :firstly,through its ability to analyze relatively intractable materials without the need for special sample preparation; secondly, through its surface sensitivity. It must be emphasised as well that with XPS are abstracted not only the surface properties as known, but also the bulk properties sometimes unavoidable depending upon the sample preparation. As more is learned about how the surface chemisuy of polymers can play an importantrolein the studies offlameretardantsystems, the more individual problems can be tailored to maximize better understanding offlameretardancy.thegoal of this article is trying to abstract more experimental data of likely processes inflameretardancyof polymers at some level by XPS technique coupling with thermal analysis techniques. 0097-6156/95/0599-0518$12.00/0 © 1995 American Chemical Society Nelson; Fire and Polymers II ACS Symposium Series; American Chemical Society: Washington, DC, 1995.

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XPS (ESCA) Studies in Flame Retardancy of Polymers

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Brief Description of XPS Test Ίΐκ spectra (MgK«) woe recorded on PHI 5300 ESCA SYSTEM (PERKIN-ELMER) at 250 W (12.5 KV χ 20 mA) under a vacuum better than 10* Pa ( 10-* Ton) calibratedfayassuming the binding energy of the adventitious carbon to be 284.6 eV. Pass energy and step length were selected to be 35.75 eV and 0.05 eV respectivelyforbetter results. Specimens in thinfilmsthrough spreading a droplet of dilute solution on aluminumfoil(for example, chloroform was adoptedforEVA copolymers) woe preferred, if possible. For polyewylenes thin films of 0.1 mm thickness can be preparedfaya mixing roll and parallel platen curing m u r h i n * on a h i m t n i i m foil. Results and Discussion Thermal Degradation of Polymers upon Heating. The basic approach in the past to

the mechanistic studies of thermal degradation of polymers and polymeric composites generally invokes gas analysis primarily of the decomposition products with techniques, such as IR, NMR, MS etc. to identify the structural changes of the bulk properties. Here, we have made use of XPS to identify the surface chemistry of the solid materials, instead. Wool, a Natural Polymer. It was chosen as one example to show its thermal behaviorfollowedby XPS. Wool is a keratin protein composed of amino acids linked fay peptide bonds, of which the units are croeslinkedfaydisulfide bonds and have attached to them reactive groups such as amino, hydroxy!, sulmydryi and carboxyi. The XPS investigation (7) of the S2p, Nls, Cls and Ols spectra as function of temperature gives further quantitative awareness into thermal behavior, as shown in Table I. Table I Table I Quantitative analysis of S2p, Nls, Cls and Ols spectra asfonctionof tegp«atoe i n ^ S/N N/C O/C Temperature,°C 0.14 Room temp. 1.00 0.03 ISO 1.10 0.03 0.14 200 0.96 0.03 0.15 245 0.18 0.09 0.16 300 0.074 0.10 0.08 350 0.040 0.11 0.06 (* Reproduced with permissionfromréf. 1. Copyright 1994) shows an abrupt decrease in S/N at about 200°C and an inflection in therangeof230° 240% in fairly good consonance with datareportedby Felix, et. aL (2). The changes in N/C and S/Nratio(Table I) imply the evolution of carbon monoxide, carbon dioxide, hydrogen sulfide, hydrogen cyanide, nitric oxide and aoylonitrile as combustion products from wool on heating reported by Koroekys (3). A larger decrease in S than in Ν was noted and ascribed by the disruption of the disulphide linkage, i.e. cystine decomposition (/). There arefourtypes of sulfur-containing groups in the surface of wool, namely, -SH-, -S-S-, -SO^H and S0 " (see Table Π). Among these, mefirsttwo 2

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Nelson; Fire and Polymers II ACS Symposium Series; American Chemical Society: Washington, DC, 1995.

520

FIRE AND P O L Y M E R S II

aie receivedfromthe complex wool structure, SOf isfromwashing déteignit needed for XPS teat, and -S03Hgix>up located m the surfiice layen is due to oxidation of -S-S-. Upon heating, say from ambient temperature to 350°C, organic sulfur-containing compounds will dominate the surface at the expense of inorganic sulfur compounds till their complete disappearance. N H evolved through bond scissions of terminal amine, side-chain amine, amide groups of lysine, argmine, asparagms and ghtamine is likely to be the main gaseous product within thu temperature ra (4). The emergence of -C=N- and - O N groups can also be observed in Nls spectra at about 250°C and 350°C,respectively,(Table Π). Downloaded by NATL UNIV OF SINGAPORE on March 27, 2017 | http://pubs.acs.org Publication Date: July 21, 1995 | doi: 10.1021/bk-1995-0599.ch032

3

Table Π Quantitative analysis of S2p and N l s spectra as function of température» Temperature, °C Atomic concentration, % S2£ Nls -SH- -S-S- -SOJH SO> -NH-CO- -NH, -Q=N* -0*Ν* Room temp. 11.0 iô.é i l l 40Λ 773 H j = =~ 130 17.8 14.5 51.4 16.3 77.0 23.0 200 15.0 14.2 52.9 17.9 58.9 41.1 — — 245 37.0 17.8 31.0 14.2 52.5 22.7 24.8 — 300 51.0 39.0 10.0 0.0 39.2 26.2 34.6 — 350 60.9 39.1 0.0 0.0 35.0 25.2 25.9 13.9 • Reproduced with permission ftomref.l. Copyright 1994 EvidencedfayIR b

The Study of Flame Retardant Mechanism in Gas Phase. Polypropylene (PP), Dechlorane Phis 25 (De-25) and SbÔj of commercial grade were used as a model system for the study of syneigy between chlorine-containing flame retardant and antimony trioxide in gas phase with the aid of XPS (5). For comparison with De-25, BCPD (a chlorine-containingflameretardantwith cyclic structure) was synthesized in the laboratoiy. Theformulationswere processed at 170 °Cfayblending as shown in Table UL A drastic change in the electronic state of the chlorine atom in systems K - l to K-4 was carefully explored as function of temperature.

Μα K-l K-2 K-3 K-4

Formulation PP+BCPD PP + BCPD+SbjOj PP +DE-25 PP+De-25 + SbA

31:14.5 31:14.5:4.5 31:14.5 31:14.5:4.5

Taking note of the change in electronic state of CI atom blended in polymeric matrix C12p spectra have beenrecordedas function of température. The ionic component, CV% observed from the spectrum can be used as an indicator in halogen-containing systems to follow thereaction.The dependence of atomic concentration (AC) C P % in systems K - l through K-4 upon temperature is shown in Figure 1. As seen, the CP-% first decreases to a minimum (for BCPD (K-l, K-2) at ca. 290°C ;forDe-25 (K-3, K-4) at ca. 320°C), then rises again due to the decomposition of both BCPD and De-25


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521

during beating. Itfollowsthat the higher the temperature at the irrimmum occurs, the better the thermal stability of theflameretardant. The significance is twofold : firstly, the emergence of ClHmks up with the interaction between FP and the radical CI* which induces again the evolution of HQ giving a subsequent impetus to the catalytic degradation of PP, secondly, on exposure to heat in afireenvironment the combination between HC1 and S b ^ leads to theformationof antimony oxychlorides and then SbCl , bom of which have r^ved to also worm noting that the separation between the curves of K-3 and K-4 is much larger than those between K-l and K-2, indicative of the fact that the system of SbpyDe^S exhibits stronger synergistic effect man that of SbPj/BCPD system in good conformity with our thermal data (/). Through XPS analysis we have the ratio Cl/Sb = 4-7 in the temperature of 260°-320°C (see, Table IV) comparable to the result of Costa, et al.(d), if the huge difference in the experimental conditions between TGA and XPS is taken into account Another point of interest is that theratioCIVSb of the intermediate antimony axychlorides, which is possibly a catalystforcharring in the condensed phase, lies inbetween the range of 0.7-1.2, implyingformulaesomething between SbOCl and Sb 0 Cl .


3

4

5

2

Table IV Total atomic coaptations of Cl, CRand Sb m me surface within therangeof260°-32Q°Cforsystem K-4 Temperature, °C Total CI % Cm Total Sb% Cl/Sb CIVSb 260 0.77 0.14 0.19 4.1 0.74 320 L24 0.22 0.18 6.9 1.20 (· Reproduced with permission from ref.5. Copyright 1991) The Study of Flame Retardant Medumism in Condensed Phase. Zirpro process (zirconium and titanium treatment) is an effective and durableflameresistance technique with keratinousfibressuch as wool, mohair, silk, cashmere and speciality animalfibres.Mam/ patents have appeared since 1970s; however, few is known of its mechanism, because the zireooyl (or titam/1)fluoridescan not easily be analyzed with reasonable accuracy. TheTOA-DTOcurves of the Zirproflameretardant prepared by Zirpro process are shown in Figure 2 (/), where there are three peaks with at 250°C,350°C and 500°C , respectively. To ascertain the stnicture of 2&pro retardant, the stokmometry has been derivedfayXPS to be F/N : N/Zr : F/Zr : O/Zr : C/Zr = 1.8 : 1.1:2.0 : 3.6 :6.8. Among those, Q/Zr and C/Zr do contain contribution from contamination In the presence offluorides,the structura of Zirpro flamed may be presumed as shown in Structure 1. The oxidation state of Zr(TV) with coodination number offiveis expected to be d° configuration. Based on this structure we have tried to study the changes in the OZr, O/Zr, F/N, N/Zr and F/Zrratiosas fractions of temper 3 and 4). Some conclusions can be readily drawn asfollows: (1) Cls spectra of Zirproflameretardant show that organic moiety begins to decompose at 150°C, with the evolution of water and carbon dioxide; (2) Both F/N and N/Zr change inversely as a function of temperature, resulting in a constantratioof F/Zr ( close to 2.0), indicative of a fact that the NH^ moiety starts decomposing at a temperaturerangingfrom300°C to 350°C. Items 1 and 2 are in excellent agreement with TOA-DTO and DTA data (omitted for simplicity); (3) The fiuorozirconate gradually losesfluorideduring heating above 350%. It is dear that there are drastic



522


0

150

200

250

300

350

400

Temperature ( V )

Figure 1 Tflbe dependence ofCl*% in systems K-l, K-2, K-3 and K-4 on temperature (Reproduced with pennissionfromref.5. Copyright 1991 Elsevier Science Ltd)

Temperature (*C)

Figure 2 TQA-DTA curvesfcrZiiproflameretardant (Reproduced wimpemussion from re Copyright 1994 Elsevier Science Ltd)


WANG


/

V

Ni-


Ο

ο

0

NH+

ç=oi

ι—\ Structure 1

Figure 3 Degradation curves of Zirpro flame retardant on heating (XPS )


524


changes in percentages of -COOH and N H / starting at about 150°C and 300°C, characteristic of decarboxylation (150°-280°C) and deaminatiofi (300°- 380°C), respectively; (4) Of great significance is theratioof F/Zr which remains constant (2.0) over a widerangeof temperaturefromambient temperature to 350°C, confirming that ZiOF (or TiOFj) may be the reactive intermediate responsiblefordie char formation, evidenced by chemical shift of 0.6 eV in C Is spectra.


2

The Stroctural Analysis of Intractable Intermediates. Melamine and its salts are widely used in thefonnulationof fire retardant additive systems for polymeric ma terials. For understanding the mechanism of melamine decomposition upon heating the problem can hardly be of access without the structural information of condensates formed on heating at temperatuie above 300°C.As a matter of fact, little is known about its mechanism of action upon heating except undergoing condensation with elimination of NHândformationof insoluble products, of which die vefy sparse solubility of these products is a major drawback encountered in their stroctural investigation. Discrepancies arose in literature that they have been given the conventional names, "melamine", "melam", "mekm" and "melon" before reaching wide agreement on their stnictures (7). The structures of melamine and melam have been well established to be s-triazme-Hke and dimer, of which the empiricalformulaewere detennined to be C^^hieand C^H^^respectively.The XPS data give us the apparent quantitativeresults,see Table V (Wang, J. Q., Costa, L., Xiang, W., Camino, O., et aL, to be submitted). Using Nls spectra one can clearly see the stoichiometrics of functional groups within both compounds which are in complete agreement with the well established stnictures. From the view-point of surface chemistry the stoichiometrics seem not to be dependent too much on oxidation in case of both compounds. Table V Curve-ffoinga of Nls and Cls spectraformelamine and melam Nls Cls Stak&iomeuy " Compound in Nls group BE,eV % group BE,eV % -OH4P2 -C=N 398.1 5235 C-C 284.6 ΪΓ4 Melamine (C#tfS^ -NH2 398.9 48.2 C=N 287.5 52.9 1 1 -C=N 398.0 Meiam (Cîu)

54.6

C-C 284.6

48.4 .C-IL-SLHÎLH

-m

399.0

36.4

£*N 287.5

46.3

-NH

400.1

9.0

C-O 288.0

5.3

2

6

4

1

Presumed Stnictures for "Melem" and •'Metal" Based on Theoretkal Analysis. The correlation between binding energy and net charge of nitrogen atom requires substantiation based on theoretical calculation (CNDO-2) before getting to the heart of the structural argument of both "melem"and "melon". The extrapolated binding energyfor^groupwasfoundto be 400.7 eV by the author, based upon which curve-


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525


fittings of Nls spectra of "mekm'and "melon" were cautiously performed (see Table VI). Hie presumed structures for "melem'and "melon" is likely as proposed in Table Vu (Wang, J.Q., Xiang, W., Costa, L. and Qimmo, G., to be submitted). TabkVI Curve-fitting re«uhs of Wem'tod "meko" StokhiomeuyinNU Nls Cls Group BE,eV % group BE,eV % C=N_ : K H : -C=N 398.2 65.2 C-C 284.6 5Ô.1 -NH 398.8 11.2 Ç-N 287.6 49.9 6 : 1 : 1:1 "mekn" -ÎJH 399.9 11.7 J§U 400.5 11.9

m • AL

Compound

2


2

-C=& 398.3 72.8 -NH 398.9 6.0 2

&c

284.6 287.6

38.7 61.3

"melon"

12 : 1

:

2.5 : 1

-NH 400.0 15.2 400.8 6.0 Charring Process in Condensed Phase— Transition Temperature, ( T ) . hi the wake of the rapid development in science and technology of polymer flame retardation an insight into the mechanisms offlameretardancyin condensed phase becomes one of thefocussingprints at issue. How to characterize and trace experimentally the c h ^ prior importance. Krevekn (8) found that there is a very significant relation between the pyrolysisresidue(%) and the Oxygen Index (OI) of a polymer, i.e. the higher the char residue, the lower theflammability.IU-defined is the char, of arbitrary definition Therefore, an alternative parameter T has been supplementally defined in the laboratory (9) as a temperature at which transition between the mescphase and the graphmc phase ofthe char takes place. r

v

E V A Copolymers as Model System for Charring Study. Compounds based on ^hybne-vinji acetate (EVA) copolymers can meet stringentrequirementsin the area, for instance, of halogen-freeflameretardant cable jackets. To begin with, thermal data for EVA copolymers derivedfromTGA are shownfirstin Table VUL The Cls spectra and valence bendsforEVA with \5% VA, for exanmfe, are shown in Figures 5 and 6 at different temperatures. Ihe small peak appeared at the higher binding energy relativetothe mam peak m Cls spectra^ to Ac (CH3COO) group attached to the backbone. It disappears at 360°C ( cf. T =359.1°C for the 1st peak), meaning the loss of the Ac group through scission of C-O bond. The Cls spectrum at 500°C displays a stupendous change in shape, ie. tailing at left side on the one hand and shifting of the main peak towards rightfayca. 2.6 eV on the other hand. An obvious change can also befoundin the valence band where the two bands positioned within the ranges of 0-20 eV and 22-29 eV (see, Figure 6) are thefingerprintsof me polydlryknic backbone and pectivety. Similar to the C l s spectrum.the band corresponding to the Ac group in valence band disappears at 360% as well. Both valence bands and Cls spectra at mec


526

FIRE AND POLYMERS II

100

2nd peak'

1 st peak 80


60

40

Ambient

150

200

250

300

Temperature C C ) +

Figure 4 Atomic concentration of NH, and -COOH groups in Zirpro FR vs température (XPS) (Reproduced with permissionfromref1. Copyright 1994 Elsevier Science Ltd)

Cls VA%:15 T e m p . 500. "C In A r g o n :

298.0

294.0 290.0

286.0

282.0

Binding energy ( e V )

Figure 5 Cls spectra ofEVA(15%VA) at diffi^t temperatures


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527

Table Vu The presumed structuresfor"melem"and "melon" based upon XPS data

Compound

Suggested structure

Stokhiometry - O N


Melamine

1

: - E H

1

2

:

- Î 3 P :

0

Comment M

tnazme^ring

0

NH,

XI Melam

6 NH

NH

2

"Melem"

"Melon"

triazme-ring

2

6 NH

1 0

2

H N^N^N^N^NH 2

4

1 1 1

cymeluric structure

2.5

cymeluric

2

12

1

1

+ NH

triazine 2

4Λ


528

FIRE A N D P O L Y M E R S II


Table Vm T G A data for E V A copolymers in 99.3 H N Peakl Peak 2 VA H Onset, °C Onset, «C 13

275

45

260

60

220

Assignment (TGA/FTTR)

359.1 (2.361Wmin) 354.8 (6.310Hfonm) 351.9 (8.629tt/toin) Evolution of H A c

2

474.5 (26.38Wmin) 471.6 (15.99Wmin) 473.1

370 375 370

(12.33%ωη) Chairing

500°C aie similar to the graphite-like structure (omitted for simplicity). The T * for E V A was carefully determined to be 470°C under A r (9). Comparison of the C l s spectra and valence bands of E V A s at three levels of V A % was performed at T p (470°C ) under A r protection. In Figures 7 and 8 we see that a^ % V A ) just happens to start converting by all appearances, the conversion of E V A with 60% V A is readily accomplished to the graphite-like structure; and that of E V A with 45% V A lies somewhere ihbetween. In contrast with T G A data one conclude that the scission of A c group from backbone leads to the formation of HAc, which does catalytically help hold the transition earlier, i e . causing chairing process easier. Consequently, E V A copolymers possess of higher flame retardancy than polyethylene. The OI of E V A increases linearly with the increase of V A content, Le. the slope » 40.22% OI / 1% V A (JO). Rationalisation was carried out by Meiserweimer (//) i n terms of enthalpy argument on the basis of a linear relationship between combustion enthalpy and V A content Looking over our XPS data the problem does not seem to be so simple as expected before. Keeping T G A data in mmd (the decrease rate of T ^ v s V A % » -0.16°C / 1% V A ; weight loss rate vs V A % - -K). 14% / mm / 1% V A ) our X P S study has shown that the A c group attached to the polyethylene backbone expedites the formation of the graphite-like structure with highly crosslmked network, which plays a very important rdb m c h a r r i ^ The Role of Oxygen. Although all polymers degrade at high temperatures i n the absence of air, degradation is almost always faster in the presence of oxygen Table I X ( Tu, H . B . & Wang, J. Q., to be submitted) gives thermal data of E V A copolymers in absence and presence of oxygen, respectively. The char residues at 500°C were measured by TGA for systems E V A , E V A / P and E V A / A F P , see Table X (Jiang, Q. J., & Wang, J. Q., to be submitted). Promoting Charring. It is evident that E V A copolymers themselves alone do not form char at all at 500°C (see Table X ) within the detectable limit in T G A unlike that observed i n X P S under inert gas. In X P S experiments run at 500°C a graphite-like structure of the residues even in very little amount can be clearly observed without any difficulties. The presence of oxygen enhances char formation through initiating K

the chairing reaction at a lower temperature, as indicated by Δ2 -60°C in the case of E V A (15 % V A ) , for instance. Even a tiny amount (e.g. 0.5%) of oxygen in air can be sufficient for a substantial depression in the average transition ternperature Tgr of β


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VA%:15 13.6

T e m p . s500"C In A r g o n

24. 3


T e m p . s460*C In A r g o n

Temp. 3 6 0 Χ In A r g o n :

R o o m temp In'Argon

40.0

32-0

24.0

16.0

8-0


Figure 6 Valence bande of EVA at different temperatures

Cls T e m p . :470"C In A r g o n

298.0

294.0

290.0

286.0

282-0


Figure 7 Cls spectra of EVA at 470°C


529

530


the char unambiguously observed by XPS (cf. Table XI). Thisfeetcan be seen more pronounced in oxygen-free polymers, for example, potyethyicnee (see below) than oxygen-containing polymers,forexample, EVA copolymers. Table DC TGA data of EVA copolymers under VA% m/n* by weight An 15 17.4 336.1 359.1 -23.0 45 3.8 336.1 354.8 -18.7 60 2.0 327.4 351.9 -24.5 Downloaded by NATL UNIV OF SINGAPORE on March 27, 2017 | http://pubs.acs.org Publication Date: July 21, 1995 | doi: 10.1021/bk-1995-0599.ch032

σ^,^

ν

• EVAfoanula:-(C^CH^-(CH^ÇH^-

;

and Air atmospheres

σ^,^ Air 415.4 438.5 450.0

V

N 474.5 471.6 473.1

*Δ-σ*.,)*-

2

480 EVA(60%) + P EVA (15%)+APP 400 460 EVA (45%) +APP 460 EVA (60%)+APP • Ρ„ APP : at a level of 10 % by weight based on elemental Ρ for each 2

X

X

Polyethylene (HDPE, LDP£) / Inorganic Phosphorus ( P APP). These systems merit our attention whether in research or application*. Inorganic phosphorus flame retardants including elemental red phosphorus (PJ and ammonium polyphosphate (APP) occupy an important position in modernflameretardation.A wealth of literature had appeared in succession. Many of the ideasrelatingto the mechanism of flameretardationby phosphorus compounds still lack definite experimental proof. A l l of our data derived from TGA of PE, PE/P and PE/APP are listed in Table ΧΠ. Figures 9 and 10 give Cls spectra of HDPE at din%«^ tenperatures umferN and ak atmosphere. The similar spectra of LDPE, LDPE/P^ LDPE/APP were omittedforsim9

X

2



WANG



Figure 8 Valence bauds of EVA at 470°C

294.0

290.0

286.0

282.0


Figure 9 Cls spectra ofHDPE, HDPE/P^ HDFE/AFP at different temperatures under N 2



532



FigurelO Cls spectra of HDPE, HDFE/P*, HDPE/APP at difiReraot temperatures under air


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WANG

Air N T„« N Air °C % % HDPB 0.4 0.0 468.0 90.0 5.5 339.2 1.9 6.8 HDPE/P 464.1 395.1 21.5 7.5 HDFE/APP 470.3 16.3 4.5 8.5 428.8 10.5 LDPE 0.4 0.0 78.0 455.9 14.0 337.2 0.0 4.1 464.0 10.0 379.3 41.5 LDPBP LDPE/APP 465.8 17.1 4.0 412.5 17.0 15.5 • T^gg : maximum temperature al thefirstpeek; A W : weight loss % at tempaature t. b Char residue 2

Sample

2

X


X

t

phcity. TGA data (cf. Table ΧΠ) discloeed that in the presence of oxygen both Ρχ and APP exert an obvious stabilized effect compatible with data repotted by Petecs (12) for Ρχ. According to the method used in literature the transition temperature Tp and Δ (IV) » 0V)air - (Jffhh were acquiredforsystems of HDFE, HDFB/P^ HDPE/APP, LDPE, LDPE/P^ and LDPE/APP as shown in Table Xffl. In harmony with TGA results it indicated that adding Fx into FE matrix can cause a change in ΔΤρ of around +20°C relative to (Tp)^ (cf. Table ΧΠΓ). hi other woods, charformationwas postponed by 20°C relative to HDFE or LDPE In the opposite direction, however, it happened to AFP by a change in ΔΤρ of about 10° to 20°C, although APP can make PE systems more stable and larger reduction in AÇTp) (12). Β was exceptionally surprised to learn thatforporyetlryteiee without P or 140°C, if compare this with polyethylene* containing Ρχ or APP. For the latter two only a small additional change in ΔΤρ, say 20°C, can be observed. The influence of oxygen obviously plays much stronger role in charring process than P or AFP; even APP behaves more powerful in charring process than Px (see Table Xffl). Another thing is the flame retardant activity of elemwital phosphorus, which may appear somewhat unanticipated because of its highly negative oxidation enthalpy. To gain further information one needs to know the interactun occurred the surface. Curve-fittings of Cls spectra for this purpose have been carried out (cf. Table XIV). Should emphasized is the fact that the oxygernxntainirig functional groups at the surface are remarkably reduced by the presence of Ρχ. r

x

Table ΧΙΠ Influence of ηtrooephere System HDHB Η&ΗΒ/Ρχ HDPE&PP LDPE LDFE/Px LDPË/ΑίΦ ACT )»,°C -140 -120 -160 -140 -120 -ISO » A C r ^ ^ C T s r ^ ^ g r ) ^ ; Experimental errorforΔ(Γ^) :± l.O^C y

Table XIV Atomic concentration (%) offimnrionalgroups of various systems at 360°C Group HDFE ΗΡΡΒ/Ρχ HDPE/APP LDPE LDPE/F* LDPE/APP 53 03 23 3* 03 Γ\ CM) 7.0 2.4 4.5 10.0 1.5 6.1 C-O 10.6 5.7 11.7 11.8 7.2 13.1 G C , C - H 79.9 91.5 81.5 74.6 91.0 77.8


533

534

FIRE AND POLYMERS II

This is direct confirmationforthe speculation that P acts as a scavenger of oxygen containing radicals, isolating the polymeric surfacefromO2 attack. From binding energies of P2p spectra at the surface (Table XV) and infrared absorption of CO-P vibrational modes at 1090, 1190 cm* one can conclude that once the oxygen containing radicals are captured by P% it will be gradually oxidized to derivatives of phosphorous acid (P+*) and phosphoric acid (P**). The derivatives of phosphorus containing compounds do cause an intense dehydration and thus, subsequent carbonization. Besides the above mechanism some other factors must be taken into account as well, e.g. oxidativereactionsoccurring at the surface in case of APP must have tremendous effect on crou-linking with higher speed than P* It is well known that highly cross-linked network does impartflameretardanceto the polymers x


1

^

Table XV KpÔlsspecta of phosphorus «

EVA(15%VAyPx (in Ar)

500

EVA(45HVA)/APP 500 (inAr) Px room temp. APP room temp. P Oj room temp. 2

134.5

2.3

compounds inberween HP0 (metaphoephite) and H ^ 0 (phosphorous acid) 2

3

135.5

3.3

129.7 133.9 135.0

0.0 3.0 2.5

inberween Pând HjP0 (phosphoric acid) elemental phosphorus ammonium polyphosphate phosphoric anhydride 3

Cross-Jinking and Flame Retardancy. Cross-linking isrecognizedas an effective meansforflameretardationof polymère. A simple meansfordetenmmng the crosslinking has been expectedforlong. It turns ait that XPS may prove to be approach to fulfill the demand. As might have been expected, a clear-sighted description of thermal degradation of EVA copolymers under Ar atmosphere had been achieved (Wang, J. Q. A Tu, H. B., to be submitted). The absolute intensity of Cls peak must be usedforheating firm ambient through 500°C. Presenting a striking contrast to TGA data the XPSresultsdivided into threeregions,more or less, corresponding to the threeregionsin TGA can simply be stated asfollows: Decontamination. It beginsfromambient to 200°C, without weight loss detected in TGA. Contamination of both carbon and oxygen, a phenomenon specific in surface analysis.

Weak Ctas-HnHng. This stage starts at 200°C up to 450*C, with elinunation of HAc in the range of 300°C to 400°C, nearly, one hundred degrees below the onset of fito peek mTCA. There is now detectablefrom200°-300°C within the experimental etror of TGA technique, indicative of somereactionstaking place in the condensed phase. The minor cross-linking may originatefromthe C-O bond scission taken (dace at a very slightly rate, at least, in the outermost layers. Within the range of 300°-400°C occurs an elimiation of HAc, which should cause a weight loss


32.

WANG


535

and result in a sequentialreductionof intensities in Cls and Ols spectra. In fact considerable cress-linking must have happened to the polymer within this range. Higjh Cross-linking. A sudden growth of intensity in Cls spectra around Tgr=( (chairing process) induces a highly cross-linked network of the charresidue(Wang, J.Q. & Tu H.B., to be submitted). In the highly cms-linking region the surface can be abundant infieeradicals, active enough torecombinewith oxygen atoms from theresidualfragmentsof Ac groupretainedin Ar atmosphere. This is why abroad results. Downloaded by NATL UNIV OF SINGAPORE on March 27, 2017 | http://pubs.acs.org Publication Date: July 21, 1995 | doi: 10.1021/bk-1995-0599.ch032

Tnm)2 above 450°C

In summarising. The last two decades have seen a major growth in the use of surface analytical tools in materials science. XPS (or, ESCA), core spectra and valence band, were used quite common to characterize polymers, capable of accommodating intractable materials andtittleor no detrimental effect to the specimens. However, very few is known in its application to the study of flameretardancyof polymers. Based on XPS data in the laboratory exemplications are described in the paper in order to call attention to the potential utilization of the surface sensitive technique in areas relevant toflameretardnacyof polymers. Among those, charring process in condensed phase seems to be one of the most promisingfieldsin view of the current demand fer novel techniques to provide informative data in the study of the blade char or non-Mackresidualash. It is shown indeed that coupled to some other techniques XPS may manifest itself to be a means of great worm inresearchand application' of flameretardantpolymers, if used properly. Literature Cited. (1) Wang. J.Q., Feng, D.M. and Tu,H.B.,Polym.Degrad.Stab., 1994,43, 93-99; (2) Felix, W.D., McDowell, M.A. & Eyring, M., Text. Res. J., 1963,33,465; (3) Koroskys, M. J.,Am.Dyest.Rep., 1969, 58 (6), 15; (4) Ingham, P., J. Appl. Pofym. Sci., 1971, 15, 3025; (5) Wang, J.Q., Feng, D.M., Wu, W.H., Zeng, M.X. and Li, Y., Polym. Degrad. Stab.,1991,31, 129-140; (6) Costa, L., Goberti, P., Paganetto, G., Camino, G., & Sgarzi, P., Third Meeting an Fire Retardant Polymers,

Torino, Italy, Sept. 1989, pp. 19, 21-22; (7) Costa, L., and Camino, G., J. Thermal Analysis, 1988,34, 423-429; (8) Van Krevelen, D.W., Chimia, 1974, 28, 504; (9) Wang, J.Q. & Tu, H.B., in Proceedings of the 2nd Beijing International

Symposium/Exhibition on Flame Retardants, Oct.11-15, Beijing, China, 272-279, 1993; (10) Ford, J.A., in Fire Resistant Hose, Cables and Belting (International

Conference) Plastics and Rubber Institute, Science and Technology Publishers Ltd September, 1986; (11)Meisenheimer,H., Proceedings of the 138th ACS Meeting, Rubber Division, October, 9-12, 1990; (12) Peters, E.N., J. Appl. Polym. Sci., 1982, 27, 1457; (13) Wilkie, C.A., in Fire and Polymers, Ed. Nelson, G.L., ACS Symposium

Series, 425, Chapter 13, 1990. RECEIVED January 24, 1995


Studies in Flame Retardancy of Polymers - American Chemical Society

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